Polyethylene compositions containing titanium organic compounds and structures produced therefrom



states This invention relates to the manufacture of polyethylenestructures and coatings. More particularly it relates to the preparationof polyethylene film suitable for conversion to bags, containers andsimilar packages.

One of the disadvantages of polyethylene film in the packaging fieldresides in its low adhesiveness to dried ink impressions, polymericcoatings, other substrates such as glass, wood, paper, and thermoplasticfilms other than.

polyethylene. The result is that any information imatent O printed onthe surface of the polyethylene film such as instructions. advertising,trademarks or recipes are smeared or rubbed off by the normal abrasionsuffered by the film during handling. This shortcoming has been,substantially overcome by socalled printability treatments described inUS. Patents 2,502,841; 2,632,921;

2.648097; 2,668,134; 2,715,075; 2,715,076; 2,715,077 and several patentapplications disclosed hereinafter. However, these treatments in turnhave caused another problem. The ability of polyethylene to adhere toitself by the application of pressure and heat, i.e. heat-scalability,necessary in converting the film to packages, although satisfactoryprior to the printability treatment, falls below satisfactory levelsafter treatment.

The object of the present invention is to provide a polyethylenestructure, particularly film, having improved properties. Another objectis to improve'the heat-sealability of polyethylene structures withoutsacrificing the desirable properties of the polyethylene structures.Another object is to provide polyethylene structures and polyethylenecoatings having ahigh level of adhesiveness to printinginks and thelike, that can be easily heatsealed. A more specific object is toprovide a polyethylenecomposition, which when formed into a structure orused as a coating and subjected to a printability treatment, willprovide a printable and heat-scalable structure. Other objects willappear hereinafter.

The objects are accomplished by a structure formed from a polyethyleneresin having a weight average molecular weight of 15,000-3,000,000(normally within the range from 200,000 to 1,500,000) and containing asmall amount, i.e.-at least about 0.1% and preferably not more thanabout 10% based on the weight of the polyethylene resin, of a titaniumorganic compound, the titanium organic compound having a softeningtemperature no greater than the lower temperature of the crystallinemelting point range of the polyethylene resin, a normal boiling pointabove the optical melting point of the polyethylene resin, and a meltviscosity, at a temperature above 110 C., lower than that of thepolyethylene resin. The process involves uniformly mixing thepolyethylene resin with the titanium organic'compound prior to formingthe structure.

Although it is possible to-define a'melting point for the monomericadditives, the nature of the polymeric titanium organic compounds makesit possible only to specify a softening temperature rather than amelting point. Since softening temperatures is the more general termapplying to both the monomeric and polymeric additives, it will be usedthroughout the specification. The softening temperature is determined byplacing a chip of the additive on a highly polished copper block and2,084,04l Patented May 16, 1961 raising the temperature of the blockuniformly. The lowest temperature at which the additive sample leaves amolten trail when moved across the block by applying light pressure witha spatula is the softening temperature.

For polyethylene, a crystalline melting range is observed. This extendsfrom a lower temperature at which crystallites begin to disappear to theso-callcd optical melting point at which crystallites are no longerdetectable.

The preferred titanium organic compounds falling within the definitionof the invention are hydrocarboxyl and acyl titanates having thestructural formula:

where R R R and R are selected from the group consisting of hydrogen,acyl of the formula (where R is alkyl), alkyl, cycloalkyl, aryl,alkaryl, aralkyl, lactyl and l-methyl-3-oxo-l-butenyl, and x is an 1integer from 1 through 100, provided that when R; is

the R, which is alkyl, may range from l-20 carbon atoms 01 greater.

On the other hand, the generic terms hydrocarbonyl titanates and theacyl titanates include branched and cyclic structures wherein thebranching is in the titaniumoxygen chain, and where the cyclic structureis made up of titanium-oxygen segments. Such structures may berepresented by the following generic formulae:

. 3 Various nomenclature have been applied to the compounds embraced bythe terms acyl titanates. In U.S. Patent No. 2,621,195, I. H. 'Haslamrefers to compounds within this terminology as titanium acylates orcarboxylates and titanium ester-carboxylates. They are also referred toas polytitanyl carboxylates and ester-carboxylates. On the other handvarious nomenclature have been applied to the compounds embraced by theterms hydrocarbonyl titanates. In U.S. Patent No. 2,621,195, I. H.Haslam refers to the compounds within this terminology as titaniumesters or organic esters of ortho-titanic acid. Specific examples ofhydrocarbonyl titanates or the titanium esters. (organic esters oforthotitanic acid) are illustrated by the following:

v t I s):

(CHa)rCHO-+l-OCH(CHQ):

on k c m) 1 Tetraisopropyl titanate C [EH31 i raHuO-Ti-O CraHal o v aCrsHn Ti etrastearyl titanate Other titanium esters include tetramethyltitanate, tetraethyl titanate, tetraisobutyl titanate, tetra-n-butyltitanate, tetra-Z-ethylhexyl'titanate, tetraamyl titanate, tetraoctyltitanate, tetradodecyl titanate, as well as tetracyclohexyl ,titanat,tetra-phenyl titanate, etc.

Specific compounds falling under the general class of acyl tit'anate(titanium acylates or carboxylates and titanium ester-carboxylates) arethe following with corresponding structural formulae:

Hydroxy titanium stearate (a titanium acylate or carboxylate)lsopro'poxy titanium stearate (a titanium ester or carboxylate) Othertitanium acylates include hydroxy titanium oleate, isopropoxy titaniumolcate, hydroxy titanium lactate, hydroxy titanium soy acylate,isopropoxy titanium soy acylate, hydroxy titanium linseed acylatc,isopropoxy linseed some doubt about the structural formulation of thelactates of titanium, and these compounds may best be illustrated by thegeneral formula;

)z( 3 4 2)z The chelated structures may take the following form fortitanium lactate:

I cmcnondb-i cnonccm In the following table are listed the properties ofsome titanium organic compounds which fit the requirements of thepresent invention and were used in the subsequent examples.

. Softening Normal Compound Temperature 1 Boilinr Point 1 c c.) c 0.)

Tetra n-butyl titanate. below-40. above 325. Tetra isopropyltit-aunts... 20 232. Tetrastearyl titanate.. above 325. Titanium lactatebelow i does not. boll. Titanium acetyl acetonate do Do. Tetra-Z-ethylhexyl titannte. helow-25 Do. Condensed. butyl titanate (di n-butyl below25. above 325.

titanate). Stearexytitaniunt oleate .do D0. 2-ethylhexoxy titaniumolente lo Do. Hydroxytitauium stearate Do. Isopropoxytitanium stoarate.does not boil.

Softening temperatures and boiling points measured at 760 mm. of mercuryare given unless otherwise specified.

As stated previously, the titanium organic additive must be blendeduniformly into a polyethylene compothe polyethylene resin will providepolyethylene structures.

displaying a marked improvement in heat-scalability as shown by highheat-seal strength. Furthermore, the polyethylene structures are morereadily heat-sealed to form seals of substantial strength at lowerheat-sealing temperatures than used heretofore.

The most important application of this invention is to polyethylenestructures, particularly film, whose surface adhesion has been improvedby so-called printability treatment. It is believed that thisprintability treatment roughens" or modifies the surface of thepolyethylene structure to create thereon microscopic hills notdetectable by touch and not visible to the naked eye. A polyethylenefilm surface is considered to be satisfactorily .roughened if thesurface of the film contains substantially uniformly distributed hillsor mounds, each individual hill or mound having a diameter, as measuredparallel to the film surface, of at least 0.05 micron to 1 micron, andusually between 0.05 micron to 0.5 micron. The elevation or height ofthese hills or mounds relative to the flat areas, i.e., areas whichappear to be relatively untreated, is seldom greater than 02,-0.5micron, and usually not greater than 0.25 micron. As a general rule, theprintability treatments do not carve out areas of the film surface toform depressions therein, but rather form hills or mounds havingelevations relative to the untreated film surface. Besides improvingprintability (adhesion to printing inks), these treatments tend toimprove the adhesive qualities of the surface of polyethylene structuresin general. However, as mentioned previously, these treatments reducethe ability of polyethylene to adhere to itself when pressure and heatare applied.

For purposes of this invention, the adhesiveness of the surface of thepolyethylene structure may be improved -by any of a number of knownexpedients. These into Henderson; treatment in a saturated solution ofsodium dichromate in concentrated sulfuric acid, in U.S. Patent No.2,668,134 to Horton. U.S. Patent No. 2,632,921 to ,KreidL-discloses aprocess of subjecting the surface of treating the surface with ozonewhile maintaining the structure at temperatures above 150 C.; that is,the molten structure immediately after extrusion (in the air gap) may betreated wih a gas containing ozone.. This process is described andclaimed in a copending application, U.S. Serial No. 323,27l,-filedNovember 29, 1952, by L. E. Wolinski. L. E. Wolinski has other patentsand applications that involve treatment with ozone: U.S. Patent No.2,715,075 relates to treatment in the presence of ozone and a halogen orhydrogen halide; U.S. Patent No. 2,715,076 relates to treatment withozone in the presence of nitrous oxide; U.S. Serial No. 323,274, filedNovember 29, 1952, relates to treatment with ozone at a temperature ofat least 150 C. followed by quenching the structure in an, aqueoussolution containing a halogen or halogen acid; and U.S. Serial No.323,275, filed November 29, 1952, relates to treatment with ozone at atemperature of at least 150 C. followed by quenching the structure in abath containing a conditioning agent such as hydrogen peroxide, nitrousacid, alkaline hypochlorites, concentrated nitric acid or mixtures ofconcentrated nitric acid and concentrated sulphuric acid. Treating themolten polyethylene structure, maintained at a temperature above 150 C.,with nitrous oxide is described in U.S. Patent No. 2,715,077 to L. E.Wolinski. The adhesivcness of the surface of polyethylene may also beimproved by quenching a freshly extruded film in an aqueous bathcontaining a halogen or a halogen acid as described in copendingapplication U.S. Serial No. 347,- 391 filed April 7, 1953, by L. E.Wolinski. The polyethylene structure may be heated witb a specialconditioning agent such as hydrogen peroxide, concentrated nitricacid,'nitrous'acid, alkaline hypochlorites, or mixtures of concentratednitric acid and concentrated sulphuric acid, as described in copendingapplication U.S.

'Serial No. 487,701, filed February 11, 1955, by L. E.

Wolinski. The use of high voltage stress accompanied by coronadischarge, as disclosed in British Patent Nos. 715,914 and 722,875, mayalso be used. Surfaces of relatively high-density polyethylenestructures may be made more adhesive by quenching a freshly formedstructure at a temperature of at least 325 C. as described in U.S.Serial No. 506,660, filed May 6, 1955 by I. Swerlick.

Specific embodiments of the present invention are pre- 'sented in thefollowing examples. In all the examples, Bakelite DYNH3 'polyethyleneresin was used. This particular resin has its lower temperature of thecrystal 145 C.-150 C. to form a sheet of the blended composition. Thesheet was then chipped into flakes and fed into the extrusion apparatus.

The flakes were remelted in the extrusion apparatus lldunnfactured byUnion Carbide and Carbon Corp.

and extruded at a temperature of 285 C. in the form of a film through aneight inch air gap, then led over a. rotating chromium quench roll. rollwas maintained at about 50 C. by passing water heated to thistemperature through the interior of the roll.

During its passage through the air gap, the molten polyethylene filmcontaining the adc'itive underwent a printability treatment. The air gapwas enclosed by a treating chamber. An ozone/oxygen mixture, containingabout 0.4% ozone by volume, was passed through the chamber to contactone surface of the polyethylene film as described in U.S. Serial No.323,271. The ozone/oxygen mixture passed through the chamber at a rateof 1.66 cu. ft./min. while the polyethylene film was led through thechamber at about 22 ft./min.

The properties of the resulting films, compared to a control film, aregiven in the following table. Heat-seal strength was measured in thefollowing manner. The film samples were first cut into 6" squares.Squares from the same sample were then superimposed and sealed along oneedge with a steel bar 3 /2 long and Vs" wide at a temperature of 200 C.The seals were performed by using a dwell time of 0.15 second and apressure of 10 lbs/sq. in. The heat-seals were made by sealing a surfacethat had undergone a printability treatment to a surface that had not,in a direction transverse to the direction in which the film wasextruded. After heat-sealing, the connected squares were cut into strips3" long and /2 wide. The free ends of the heatseal strips were thenpulled apart in a tensile testing apparatus at a rate of per minute. Thestrength of the heat-seal, expressed in grams/inch of width, representsthe highest force necessary to pull the strips apart.

Printability was determined by applying Excelobrite" W-500, an inkmanufactured by Bensing Brothers & Deeney, to the surface of the film bya commercial ink spreader. The spreader was composed of a steel rodhaving fine wires wrapped around it and produced a plurality of finewhite lines on the surface of the film. The ink was dried by exposurefor 3 minutes to a temperature of 60 C. After the ink cooled to roomtemperature, a strip of pressure-sensitive tape was applied to the filmsurface and pressed firmly. The strip was then pulled from the surfaceof the film and examined to determine whether any ink was removed. Ifink were removed, the structure was classified as non-printable."

Table I EFFECT OF TITANIUM ORGANIC ADDITIVES ON HEAT- SEAL STRENGTH OFOZONE/OXYGEN-TREATED PRINT- ABLE POLYETHYLENE FILMS Heat-Seal ExamplePercent Additive Strength (t i l nch) None 1, 035 0.2% 2-ethylhexoxytitanium olente 1, 205 0.4% 2-ethylhexoxy titanium 0loate. 2, 1.0%Z-ethylhexoxy titanium oleate 1, 473 0.4% Hydroxytitauiurn steurute 1,750 1.0% Hydroxytlttmium stcarate. 1, 400 0.4% Isopropoxytitauiumsteer-ate l, 385 1.0% Isopropoxytitunium stearnte 1. 445 0.4%Tetrastearyl titanute 1, 0.4% Tetra-Z-ethyl hexyl titanute 1,300 0.4%Condensed butyl tltnuate. 1,370 0.4% Tetraisopropyl tltunate... 1, 7350.4% Titanium lactate 1, 795 0.4% Titanium acetyl aeetonate 1, 735

EXAMPLES 14-30 Polyethylene films were prepared in the manner describedfor Examples 1-13 except for the concentration The chrome quench 1 7 ofozone used in the printability treatment. About 1.2% by volume of ozoneinstead of 0.4% was used. The properties of the resulting films,compared to a. control, are given inthe following table.

Table II EFFECT OF TITANIUM ORGANIC ADDI'IIVEB ON HEAT- SEAL STRENGTH OFOZONE/OXYGEN-TREATED PRINT- ABLE POLYETHYLENE FILMS i Heat-Seal ExamplePercent Additive Strength (grams/ inch) Control None 476 14 0.2% Tetrari-butyl titanate 1, 135 0.4% Tetra n-butyl titanate 1, 305 1.0% Tetran-butyl titanate 800 0.2% Condensed butyl t.tanate. 939 0.5% Condensedbutyl titanate. 939 0.2% Tetra stearyl titanate..- 7 0.5% Tetra stearyltitanate 812 0.3% Tetra isopropyl titanat 052 0.5% Tetra isopropyltitanate.-- 1,090 0.3% etra-2-ethylhexy1 titanate 1, 305 0.5%Tetra-aethylhexyl titanate 757 0.3% 2-ethy1 hexoxytitanium ole'nte 1,090 0.5% 2-ethyi hexoxytitanium olente- 854 0.3% Titanium lactate 7990.5% Titanium lactate 1, 330 0.4% Stearoxytitanium oleate. 1, 150 301.0% Stearoxytitanium oleate 1, 100

EXAMPLES 31-43 Polyethylene films were prepared in the manner describedfor Examples 1l3 except for the printability treatment. A mixture ofozone/oxygen/chlorine was used as described in U.S. Patent No. 2,715,075instead of the ozone/oxygen treatment. The concentrations of ozone andchlorine in the mixture were each 0.4% by volume. The properties of theresulting films, compared to a control, are given in the followingtable.

I Table III EFFECT OF TITANIUM ORGANIC ADDITIVES ON HEAT- to 43 0.4%Titanium acetyl acetonate EXAMPLES 44-58 Polyethylene films wereprepared in the manner described for Examples 1-13 except for theprintability treatment. A mixture of ozone/oxygen/chlorine was used asdescribed in U.S. Patent No. 2,715,075 instead of the ozone/oxygentreatment. The concentrations of ozone and chlorine in the mixture wererespectively 1.2% and 0.8% by volume. The properties of the resulting HOF OZONE4OXYGEN CHLORINE- TREATED PRINTABLE POLYETH LEN E F1 MSHeat-Seal Example Percent Additive Strength (grams/ inch) None 238 0.2%Tetra n-butyl titan 630 0.47 Tetra n-butyl titanate 379 0.2%; Condensedbutyl titanete 601 0.5% Condensed butyl titansto 671 (1.27 Tetra stearyltitanate..- 783 0.5%; Tetra stearyl titannte-.- 924 0.3% Tetra isopropyltitanate. Z58 0.5% Tetra isopropyl titanate 0 17 0.3% Tetra-2ethylhexyltitanate 700 0.3% 2ethyl hexoxytitanium olente 532 0.5% 2-ethylhexoxytitanium oleate 364 0.3% Titanium lactate 1,150 0.5% Titaniumiaetate 1, 175 0.4% Btearoxytltanium oleate 910 1.0% Stearoxytitaniumoleate 868 additives were prepared and melt extruded in the form of afilm through the air gap then over a rotating chromium quench roll as inExamples 1-13. However, the ozone/oxygen treatment was omitted. Insteadthe film was treated at a speed of ft./min. with a propane/air demo at aflame temperature of about 1900 C., the burner being about from thesurface of the film. The top surface of the film attained a temperatureover 200 C. while the under surface passed over the chromium rollmaintained at 2 C. The details oi this printability treatment are givenin U.S. Patent No. 2,648,097.

The properties of the resulting printable films, compared to a controlfilm that contained no additive but received the flame treatment, aregiven in the following table. The heat-sealstrengths were measured bysealing a treated surface to a treated surface, the seals being made inthe direction in which the film was extruded at the temperature shown inthe table. The seals were pulled in the direction transverse to that ofextrusion.

In all other details heat-seal strength was measured substantially asdisclosed previously.

Hen t-Senl Strength (grams/inch) Using Various Sealing Percent AdditiveTemperatures Example EXAMPLES 61-62 Blends of polyethylene resin and theadditives were prepared and melt extruded in the form of films throughthe air gap then over a chromium quench roll at 60 C. as in Examples1-13. However, the zone/oxygen treatment was omitted. Instead, the filmwas fed onto a grounded steel drum rotating at a circumferential speedof 35 ft./minute. A Tesla coil was held A3 above the drum and discharged30,000 volts across the width of the polyethylene film in a mannersimilar to that described in British Patent No. 715,914.

The properties of the resulting printable films, comcomparativepurposes.

pared to a control film that contained no additive but received theelectrical discharge treatment, are given in the following table.Heat-seal strength was measured as in Examples59-50.

Table VI EFFECT OF TITANIUM ORGANIC ADDITIVES ON HEAT- SEAL STRENGTH OFVOLTAGE-TREATED PRINTABLE POLYETHYLENE FILMS Heat-Seal Strength(grams/inch) Using Various Sealing Temperatures Example Percent AdditiveNone 0. Titanium lactate" 0. 4% Tetra u-butyl titanate...

EXAMPLES 63-65 Polyethylene films containing titanium organic additiveswere prepared in the manner described for Examples l-I3-except that theozone/ oxygen treatment was omitted. In this example, the films did notundergo any printability treatment. The results, compared to a controlwherein no additive was used, are given in the following table. Theheat-seal strengths of two commercial polyethylene films (Products X andY), containing no additives of the type disclosed herein, are also givenfor Table VII EFFECT OF TITANIUM ORGANIC ADDIIIVES ON HEAT-??EfigSTRENGTH OF NON-PRINTABLE POLYETHYLENE As shown "by the examples,the invention is not only useful in preparing heat-scalable, printablepolyethylene packaging film, but is useful in improving the heat-sealstrength of polyethylene film in general, and in lowering thetemperature required for satisfactory heat-seals. In the case ofprintable polyethylene packaging films, the addition of the specifiedtitanium organic compounds in acfcordance with the invention serves torecover the heat seal strength lost by the polyethylene film due to theprintability treatment. The use of these special additives also tends toretard the loss of printability of heat-sealability of the polyethylenefilm with age such as inevitably occurs during storage prior to printingand conversion of film to bags. Although the description has beenrestricted to the use of titanium organic compounds, zirconium organiccompounds within the same definition as the titanium compounds will alsooperate for the purposes of the, present invention.

Besides polyethylene film, the invention is applicable to otherself-supporting structures such as filaments, rods, tubes, sheets forlamination and to supported polyethylene structures wherein polyethylenecompositions containing the additives are coated on one or both sides ofvarious base films such as cellophane, polyethylene terephthalate,polyvinylidene chloride, etc. It is applicable to polyethylenestructures of normal density (0.91- 0.93 gram/cc.) and to polyethylenestructures of heavy density (0.94-0.96 gram/co); to polyethylenecompositions formed by copolymerizing polyethylene with minor amounts ofpropylene, butylene, isobutylene, styrene, vinyl-acetate and similarvinyl compounds; to polymethylene derived from carbon monoxide andhydrogen as in U.S. Patent No. 2,652,372 to Farlow and Herrick; and topolypropylene, polybutylene and the like.

In forming polyethylene films containing the special additives, a meltextrusion process is usually employed. In general, a molding powder orflake of polyethylene along with the additive is fed continuously into amelt extrusion machine; the molten polyethylene is continuously extrudedthrough a slot orifice, then through an air gap vertically downward intoa quench bath or onto a quench roll maintained at a temperature from 25C.- (1., preferably from 30 C.60 C. Usually, the polyethylene isextruded from a melt maintained at a temperature above C. Tubing isusually extruded from a melt at a temperature within a range of 150 C.-200 C., whereas film is extruded at a temperature which may be anywherefrom above 250 C. to the degradation temperature of the polyethylene. Analternate process of forming polyethylene film which also employs moltenpolyethylene comprises milling molten polymer on closely spaced calenderrolls to form a film which is conducted vertically downward into aquench bath. In either of these general methods of forming polyethylenefilm, the space between the point where the molten film leaves the slotorifice or the last calender roll and the point where the molten filmenters the quench bath is termed the air gap. During passage through theair gap, the film is usually permitted to pass uninhibited through theatmosphere; and thisprovides for some superficial cooling. Generally,the length of the air gap ranges from 2" to as long as 15 in some cases.In some cases as illustrated in Examples l-58, the film may be subjectedto the printability treatment in the air gap. Besides formingpolyethylene structures from the molten polymer, polyethylene structuresmay also be formed from solutions thereof in a solvent, or fromdispersions of the polyethylene in an inert liquid medium such as water.Similarly, the

polyethylene coatings may be applied upon other substrates from a melt,solvent solution or dispersion in a liquid medium.

The amount of additive required lies above about 0.1%, and very rarelyabove 10%. The precise amount will depend upon the increase in heat-sealstrength desired. In cases where it is desired to recover the heatsealstrength lost by the printability treatment, the amount of additive willdepend on the particular printability treatment and the extent of thistreatment. In most cases, not more than about 5% of the additive need beincorporated in the polyethylene film to prevent the subsequent loss ofheat-seal strength due to the printability treatment.

The following theory is offered to explain the surprising success of thepresent invention. However, this theory should not be construed aslimiting the scope of the invention. It is believed that the additivewhen incorporated in the polyethylene composition is: not completelycompatible with the polyethylene resin. During the heat-sealing step,the additive tends to exude to the surface, thus plasticizing thesurface of the polyethylene structure. Plasticization of the surface, inturn, serves to increase the heat-scalability of the structure.

As many widely different embodiments can be made without departing fromthe spirit and scope of this invention, this invention is not limitedexcept as defined in the appended claims.

What is claimed is:

l. A composition of matter comprising a polyethylene resin having aweight average molecular weight of 15,000 to 3,000,000 and 0.1%-10%,based on the weight of said sented by the structural formula: v I p in vv .l 111-0 m- R, 0

I Rs X where R,, R R and R are selected from the group consisting ofhydrogen, acyl of the formula RC=O (where R' is alkyl), alkyl,cycloalkyl, aryl, alkaryl, aralkyl, lactyl and l-methyl-B-oxo-l-butenyl,and x is an 'integer from l-through 100, provided that when R is lactyl,R is lactyl, R and R are hydrogen and x equals 1 and that when R, isl-methyl-3-oxo-l-butenyl, R is 1- iriethyl-B-oxo-l-butenyl, R and R arehydrogen and x equals 1, said titanium organic compound having a soft- Yening temperature no greater than the lower temperature titanium organiccompound is tetra n-butyl titanate;

V 3. A composition of matter as in claim 1 wherein the titanium organiccompound is tetra isopropyl titanate.

. 4. A composition, of matter as in claim 1 wherein the titanium organiccompound is tetrastearyl titana'te.

5. A composition of matter as in claim 1 wherein the titanium organiccompound is titanium lactate. 6. A composition of matter as in claim 1wherein the titanium organic compound is titanium acetyl acetonate. 7. Acomposition of matter comprising a polyethylene resin having a weightaverage'rnolecular weight of 200,- 000 to 1,500,000 and 0.l%-%, based onthe weight of said resin, of at least one titanium organic compoundrepresented by the structural formula:

where R R R and R are selected from the roup consisting of hydrogen,acyl of.the formula RC=O (where R is' alkyl), alkyl, cycloalkyl, aryl,alkaryl, aralkyl, lactyl and l-methyl-3-oXo-l-butenyl, and x 'is aninteger from 1 through 100, provided that when R; is lactyL-R is lactyl,R and R are hydrogen and'x equals 1 and that when R, isl-rnethyl-3-oxo-l-butenyl, R is l-rnethyl-3-oxo-1-butenyl, R and R arehydrogen and x equ'als l, said titanium organic compound having asoftening temperature no greater than the lower temperature of thecrystalline melting range of said resin, a normal boiling point abovethe optical melting point of said resin 'and a melt viscosity lower thanthat of said resin at a temperature above 110 C.

8.,A packaging firm comprising a polyethylene resin having a weightaverage molecular weight of 15,000 to 3.000,000 and 0.1 %-l0%, based onthe weight of said resin, of at least'one titanium'organic compoundrepresented by the structural formula:

12 where R R R and R are selected from the group consisting of hydrogen,acyl of the formula (where R is alkyl), alkyl, cycloalkyl, aryl,alkaryl, aralkyl, lactyl and 1-methyl3-oxo-l-butenyl, and x is aninteger from 1 through 100, provided that when R; is lactyl, R islactyl, R and R are hydrogen and x equals 1 and that when R, is1-methyl-3'oxod-butenyl, R is l-methyl-3-oxo-l-butenyl, R and R arehydrogen and x equals 1, said titanium organic compound having asoftening temperature no greater than the lower temperature of thecrystalline melting range of said resin, an average normal boilingtemperature above' the optical melting point of said resin and a meltviscosity lower than that of said resin at a temperature above C. 9. Apackaging film comprising a polyethylene resin having a weight averagemolecular weight between 200,- 000 and 1,500,000 and O.1%-10%, based onthe weight of said resin, of at least one titanium organic compounrepresented by the structural formula:

i Rs 2 where R R R and R 'are selected from the group consisting ofhydrogen, acyl of the formula (where R is alkyl), alkyl, cycloalkyl,aryl, alkaryl, aralkyl, lactyl and l-methyl-3-oxo-l-butenyl, and x is aninteger from 1 through 100, provided thatwhen R is lactyl, R is lactyl,R and R are hydrogen and x equals 1 and that when R, isl-methyl-3-oxo-l-butenyl, R is 1-methyl-3-oxo-l-butenyl, R and R arehydrogen and x equals 1, said titanium organic compound having asoftening temperature no greater than the lower tempera ture of thecrystalline melting range of said resin, an average normal boilingtemperature above the optical melting point of said resin and a meltviscosity lower than that of said polyethylene resin at a temperatureabove 110 C.

10. Self-supporting structures and coatings comprising a polyethylenecomponent having a weight average molecular weight of 15,000 to3,000,000 and 0.l%10%, based on the weight of said polyethylenecomponent, of at least one titanium organic compound represented by thestructural formula:

where R R R and R are selected from the group consisting of hydrogen,acyl of the formula 1 and that when R, is 1-methyl-3-oxo-1-butenyl, R,is

l-methyl-B-oxo-l-butenyl, R and R are hydrogen and 13 a x equals 1, saidtitanium organic compound having a softening temperature no greater thanthe lower temperature of the crystalline melting range of saidpolyethylene component, an average normal boiling temperature above theoptical melting point of said polyethylene component and a meltviscosity lower than that of said polyethylene compormet at atemperature above 110 C.

References Cited in the file of this patent UNITED STATES PATENTS2,405,977 Peters Aug. 20, 1946 14 Fuller n- Feb. 15, 1949 DAlelio Nov.28, 1950 Signaigo Apr. 24, 1951 Bruson Jan. 18, 1955 Edwards et a1. Feb.18, 1958 Heyson July 29, 1958 Anderson et al Dec. 2, 1958 OTHERREFERENCES News, volume 33, pages 4226 and 4228, October 1955.

1. A COMPOSITION OF MATTER COMPRISING A POLYETHYLENE RESIN HAVING AWEIGHT AVERAGE MOLECULAR WEIGHT OF 15,000 TO 3,000,000 AND 0.1%-10%,BASED ON THE WEIGHT OF SAID RESIN, OF AT LEAST ONE TITANIUM ORGANICCOMPOUND REPRESENTED BY THE STRUCTURAL FORMULA: